CN103923383B - A kind of polymer-based composite with excellent toughness and preparation method thereof - Google Patents

A kind of polymer-based composite with excellent toughness and preparation method thereof Download PDF

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CN103923383B
CN103923383B CN201410126676.5A CN201410126676A CN103923383B CN 103923383 B CN103923383 B CN 103923383B CN 201410126676 A CN201410126676 A CN 201410126676A CN 103923383 B CN103923383 B CN 103923383B
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polymer
composite
layer
toughness
ductile layers
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CN103923383A (en
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吴宏
王建峰
郭少云
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Sichuan University
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
    • B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/49—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using two or more extruders to feed one die or nozzle
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/302—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising aromatic vinyl (co)polymers, e.g. styrenic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/06—Polystyrene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/9258—Velocity
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/558—Impact strength, toughness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2309/00—Parameters for the laminating or treatment process; Apparatus details
    • B32B2309/14—Velocity, e.g. feed speeds

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Extrusion Moulding Of Plastics Or The Like (AREA)
  • Laminated Bodies (AREA)

Abstract

The invention discloses a kind of polymer-based soft or hard alternate multiple composite and preparation method thereof, this composite is made up of polymer-based brittle layer and polymer-based ductile layers alternately laminated, forms soft or hard multilamellar bicontinuous structure alternately. Ductile layers and brittle layer are same macromolecule matrix, and ductile layers refers to that adding toughener in brittle layer matrix carries out toughening modifying, so ensures the big poor toughness of brittle layer fragility, the little good toughness of ductile layers fragility. By in foreign impacts process, brittle layer and ductile layers support mutually, each provide toughness and the rigidity of material. Therefore the polymer-based composite that this invention is prepared for having excellent toughness and rigidity is effectively improved. The number of plies and the thickness of the polymer-based soft or hard alternate multiple composite of the present invention are controlled, and formula is adjustable; The good mechanical performance of composite; Method is simple, can produce by continuous batch, and production cost is low, can be widely applied to prepare and has the polymer-based sheet material of excellent toughness, sheet material and membrane material.

Description

A kind of polymer-based composite with excellent toughness and preparation method thereof
Technical field
The present invention relates to the processing and manufacturing field of polymer composite, particularly to a kind of polymer-based soft or hard alternate multiple composite with excellent toughness.
Background technology
Compared with other materials, macromolecular material has light weight, corrosion-resistant, specific strength is high, excellent electrical property, to be easily worked molding be the features such as various beautiful appearance, bright goods, thus as a kind of new material, that material industry is rely the indispensable important component part of development, be widely used in agricultural, fishing animal husbandry, electrically, machinery instrument, automobile, Aero-Space, national defence tip, building materials, decoration finishing, the industrial department such as medical apparatus and instruments. But, for the macromolecular materials such as such as polypropylene, polystyrene, polrvinyl chloride, poor toughness but seriously governs these materials and is more widely applied. Along with the quick development of society, people propose more stringent requirement for the toughness properties of macromolecular material. Such as polypropylene, if the toughness under its toughness especially low temperature environment is poor, then when it uses as bumper, will there is very big hidden danger. Therefore, how to improve the toughness properties of the big macromolecular material of the poor toughness fragility such as polypropylene, polystyrene, polrvinyl chloride, have become as the problem that numerous scholar endeavours to solve.
Toughening modifying currently for macromolecular material mainly includes launching from the following aspects:
1) principle that composite is modified is utilized, add elastomer in the base and carry out toughening modifying, as fine in chlorinated polyethylene, polyolefin elastomer, methyl methacrylate/butadiene/styrene copolymers, methylmethacrylate copolymer, propylene/butadiene/styrene copolymers and ethylene/acetic acid ethylene copolymer etc., or high-impact rubber, such as styrene-butadiene styrene block copolymer, EP rubbers, ethylene propylene diene rubber and NBR etc.
2) utilizing the principle that composite is modified, add organic rigid-particle in the base and carry out toughening modifying, the organic rigid-particle of selection includes polymethyl methacrylate, polystyrene, SAN etc.
3) utilizing the principle that composite is modified, add electrodeless rigid particles in the base and carry out toughening modifying, the inorganic rigid particle of selection includes acicular wollastonite, the calcium carbonate of optimizing surface process, Muscovitum etc.
3) by matrix material/elastic body toughening agent/organic or inorganic rigid particles ternary built, the toughness of matrix is improved by controlling dispersibility form.
4) chemical modification methods such as copolymerization, grafting, crosslinking are adopted to improve the toughness of matrix material.
But, the existing method modified about plastic toughening faces many problems. Such as, one, toughening modifying is carried out by interpolation elastic body toughening agent in the base, this is most common method, but, want to obtain the toughness under excellent toughness especially low temperature, it is necessary for adding substantial amounts of toughener, although the toughness of matrix material is improved, but the rigidity of matrix is but lost very big; Two, organic by interpolation or inorganic rigid particle carries out toughening modifying and mainly considers from the angle strengthened, and improves the toughness of matrix material by controlling the dispersing morphology of matrix and dispersion phase. The method modified compared to adding elastic body toughening, although the rigidity that this toughening modifying method makes material increases, but often toughening effect is general, and especially the improvement of low-temperature flexibility is worse; Three, the method adopting ternary built is the method that recently invention adopts, but, in ternary system, the control of dispersed phase morphology is highly difficult, and this makes the toughness reinforcing stability of toughened system very poor, is unfavorable for continuous prodution; The improvement of toughness and low temperature resistant fragility also can be produced good effect by the method four, adopting chemical modification, but the complex technical process of this method, relatively costly, it is unsuitable for continuous prodution.
Summary of the invention
At present, the existing method about macromolecular material toughening modifying mostly only focuses on the role of toughener in toughened system, have ignored the design of composite self structure, result is or belongs to and dig the eastern wall to repair the western one, or complex technical process, continuous prodution relatively costly, inapplicable. The present invention by the integrally-built design of composite self, has explored and has had soft or hard and replace the polymer-based composite of layered composite structure. This kind of polymer-based composite is replaced lamellar composite by polymer-based brittle layer and polymer-based ductile layers and is prepared from, and has excellent toughness and the rigidity comparatively balanced. The number of plies and the thickness of this composite are controlled, and preparation technology is simple, economical, and effect is notable, can produce by continuous batch.
This patent realizes improving the toughness of polymer matrix composite and obtaining the rigid nature of balance by techniques below principle: the poor toughness fragility of (1) brittle layer is big, the good toughness poor rigidity of ductile layers, both are when composite is subject to external influence external impacts, can mutually support, mutually supplement, the while of being material acquisition high tenacity, the rigidity of material is unlikely to too much loss. (2) due in composite matrix and toughener have the good compatibility, and brittle layer is identical with ductile layers matrix material, therefore, the interface in alternating multilayered structure thickens, play the effect connecting brittle layer and ductile layers very well, it is achieved the brittle-ductile transition of material macroscopic view.(3) due to the existence of the limited restraining structure of stratiform, comparing common blend, in alternate multiple composite, the dispersed phase morphology of toughener presents the anisotropy of obvious both macro and micro, and the toughening effect of system is produced active influence.
Specifically, this invention address that above-mentioned technical problem be employed technical scheme comprise that, the polymer-based composite of the present invention is formed through fusion plastification, n stratiform overlapping by following polymer-based brittle layer material and ductile layers material 2(n+1)Layer soft or hard co-continuous layer structure composite alternately:
(1) matrix of described polymer-based brittle layer selects the macromolecular material of poor toughness;
(2) matrix of described polymer-based ductile layers selects the polymer-based composite by after toughening modifying being toughness;
(3) the modular ratio ductile layers of this polymer-based brittle layer wants height, and ductile layers is higher than the toughness of brittle layer, and the difference of usual brittle layer and ductile layers modulus and toughness is the bigger the better.
Above-mentioned polymer-based brittle layer can be selected for poor toughness under the poor toughness such as polypropylene, polystyrene, polrvinyl chloride, polyamide, polyethylene terephthalate, polybutylene terephthalate (PBT), Merlon, polyformaldehyde, polyphenylene oxide, acrylonitrile/butadiene/styrene copolymer, polysulfones, polyethylene, high impact polystyrene, epoxy resin or special environment and needs the macromolecular material carrying out toughening modifying as matrix.
In above-mentioned polymer-based ductile layers, toughener can select hips resin, as fine in chlorinated polyethylene, polyolefin elastomer, methyl methacrylate/butadiene/styrene copolymers, methylmethacrylate copolymer, propylene/butadiene/styrene copolymers and ethylene/acetic acid ethylene copolymer, polyethylene kind elastomer etc., or high-impact rubber, such as styrene-butadiene styrene block copolymer, EP rubbers, ethylene propylene diene rubber and NBR etc.; The consumption of toughener more than the brittle-ductile transition point content of this toughened system, so should can ensure the existence of ductile layers, can successfully construct the continuous layer structure that soft or hard is arranged alternately.
Above-mentioned toughener should have the good compatibility with matrix, and brittle layer and ductile layers matrix should be same macromolecular material. Such guarantee constructs out the continuous layer structure that the soft or hard that interface seriality is good, cementability is good, intensity is high is arranged alternately.
Present invention provides the method preparing the above-mentioned polymer-based composite with excellent toughness, this preparation method directly adopt disclosed in the Chinese patent CN101439576A that the applicant applies for by extruder (A, B), allotter (C), the microbedding co-extruder that layer multiplexer (D) and outlet mold (E) are constituted, it is characterized in first preparing polymer-based brittle layer material and polymer-based ductile layers material, then polymer-based brittle layer material and ductile layers material are put into respectively the two extruders (A of microbedding co-extrusion device, B) in, after fusion plastification, make two strands of melts overlapping in allotter (C), after the cutting and superposition of n layer multiplexer (D), flow out from outlet mold (E), traction then through the compacting of tri-roll press machine and traction machine, obtain 2(n+1)Layer is by brittle layer and ductile layersContinuouslyAlternatively distributed polymer-based composite.
In above-mentioned preparation method, in soft or hard alternate multiple composite, toughener total content can be adjusted by the content of toughener in the thickness ratio of control brittle layer and ductile layers and ductile layers. And the thickness ratio of brittle layer and ductile layers is to be adjusted by the rotating ratio of control two extruders (A, B).
Patent of the present invention has the advantage that
(1) composite that prepared by the present invention forms brittle layer and ductile layers soft or hard stratiform constraint bicontinuous structure alternately, can be effectively improved the toughness of macromolecular material.
(2) soft or hard alternate multiple composite construction provided by the invention can make material when being subject to foreign impacts, and brittle layer and ductile layers support mutually, mutually supplement, and makes material obtain toughness and the rigidity of balance.
(3) ductile layers in the composite of the present invention and brittle layer belong to a kind of matrix material together, and matrix material is good with the toughener compatibility, and interfacial bond property does not well have lamination.
(4) preparation method of the present invention adopts the one-shot forming technique preparation method technique that lamellar composite is extruded simple, convenient operation and control; By regulating and control the extrusion rotating ratio of two extruders, it is possible to adjust the thickness of brittle layer and ductile layers; By controlling the quantity of increase and decrease layer multiplexer, it is possible to regulate the number of plies of alternate multiple material.
Visible, the polymer-based composite excellent material performance of soft or hard alternating multilayered structure provided by the invention, cost is low, preparation method technique is simple, convenient operation and control, production efficiency is high, and production cost is low, there is wide industrialization and market prospect, it is possible to be widely used in preparing there is the polymer-based sheet material of excellent toughness, sheet material and membrane material.
Accompanying drawing explanation
The present invention is further illustrated below in conjunction with accompanying drawing.
Fig. 1 is the structural representation of microbedding co-extruder involved in the present invention. In the drawings, A, B: extruder, C: allotter, D: layer multiplexer, E: outlet mold.
Fig. 2 is the structure enlarged diagram of the polymer-based composite of soft or hard alternately laminated structure prepared by the present invention. In the drawings, F: brittle layer, G: ductile layers.
Specific implementation method
Be necessary it is pointed out here that, the following examples are further illustrating the present invention, it is impossible to be interpreted as limiting the scope of the invention, and the present invention can be carried out some nonessential improvement and adjustment according to the invention described above content by person skilled in art.
Embodiment 1
(1) select polypropylene (PP) (1300, Beijing Yanshan Petrochemical) as brittle layer matrix material. By double screw extruder extruding pelletization, dry.
Double screw extruder extruding and pelletizing process parameter:
Processing temperature sets: a district, 2nd district, three district's temperature respectively 170,190,200 DEG C, and head temperature is 193 DEG C; Screw speed: 350 revs/min; Feeding: 10Hz; Pelleter pulling speed: 60-70 rev/min.
(2) selecting polypropylene (PP) (1300, Beijing Yanshan Petrochemical) as matrix material, polyolefin elastomer (8150, Du Pont) is as toughener, and PP/POE mass proportioning is 70:30. Through double screw extruder extruding pelletization, drying, preparation PP/POE blend is as ductile layers.
(3) fragility PP and toughness PP/POE blend are put into respectively in the extruder A and extruder B (see Fig. 1) of the microbedding co-extruder being made up of extruder A, B, distributor C, layer multiplexer D and outlet mold E disclosed in Chinese patent CN101439576A, the rotating ratio regulating PP brittle layer and PP/POE blended layer extruder is 5.5:7.0, and each section of temperature of extruder controls respectively at 160-200-215-215 C and 90-200-215-215 C. After material melts plasticizing in extruder, two strands of melts are made to overlap in distributor C, flow out from outlet mold E after the cutting and layering superposition of 6 layer multiplexer D, wherein distributor C, layer multiplexer D and outlet mold E temperature be about 210 DEG C, traction then through the compacting of tri-roll press machine and traction machine, can obtaining 128 layers from outlet mold extrusion and replace laminar composite (referring to Fig. 2), after testing, in this composite, the total content of toughener POE is 18wt%.After testing, low temperature (-40 C) impact strength of this composite is 6.5KJ/m2, bending strength is 29MPa, and hot strength is 34MPa.
Comparative example 1
(1) selecting polypropylene (PP) (1300, Beijing Yanshan Petrochemical) as matrix material, polyolefin elastomer (POE) (8150, Du Pont) is as toughener, and PP/POE mass proportioning is 80:20. Through double screw extruder extruding pelletization, dry, prepare PP/POE blend.
(2) use an extruder A in microbedding co-extruder disclosed in Chinese patent CN101439576A, close extruder B. The PP/POE blend that quality proportioning is 80:20 is implanted sequentially extruder A, and the rotating ratio controlling extruder A is 5.5, and each section of temperature of extruder controls respectively at 90-200-215-215 C. After material melts plasticizing in extruder, make melt after flowing through distributor C, flow out from outlet mold E after the cutting continuously and layering superposition of 6 layer multiplexer D, wherein distributor C, layer multiplexer D and outlet mold E temperature be about 210 DEG C, then through the traction of the compacting of tri-roll press machine and traction machine, the common PP/POE blend from outlet mold extrusion can be obtained.
Then adopt identical condition, prepare the common blend of PP/POE that POE content is 30wt%. After testing, POE content is low temperature (-40 C) notch impact strength of the common blend of 20wt% is 3.7KJ/m2, bending strength is 26MPa, and hot strength is 29MPa; POE content is the low temperature notched impact strength 6.6KJ/m of the common blend of 30wt%2, bending strength is 24MPa, and hot strength is 24MPa.
Performance comparison from above-described embodiment 1 and comparative example 1, POE total content is the low temperature notched impact strength low temperature notched impact strength close to the common blend that POE content is 30wt% of the soft or hard alternate multiple composite of 18wt%, far above the low temperature notched impact strength of the common blend that POE content is 20wt%. and the bending strength of the soft or hard alternate multiple composite that POE total content is 18wt% and hot strength are also high than the bending strength of the common blend that POE content is 30wt% or 20wt% and hot strength. This is mainly due to the alternately existence of brittle layer and ductile layers, make material in the process being subject to foreign impacts, brittle layer and ductile layers support mutually, mutually supplement the performance that another layer lacks, making material while obtaining excellent low-temperature impact toughness, the rigidity of material have also been obtained good maintenance. Being additionally, since in polypropylene-base alternate multiple blend has hundreds and thousands of interface layer by layer to exist, and the bed boundary compatibility is good, cementability is strong, interface interaction power is big, and when being subject to extraneous drawing force, the existence of interface interaction imparts the tensile property that alternate multiple blended compound material is more excellent. Brittle layer prepared by the present invention and ductile layers replace the behavior of polypropylene composites of stratiform arrangement and achieve low temperature brittle-ductile transition under relatively low POE content, impart the low-temperature impact toughness that composite is more excellent, and the layer structure that soft or hard is arranged alternately also makes material while obtaining excellent toughness, maintain good rigid nature, it is thus achieved that the behavior of polypropylene composites of excellent combination property. The formula of embodiment 1, Thickness ratio and the number of plies can be adjusted according to actual needs, and then obtain the polypropylene-base soft or hard alternate multiple composite of different toughener POE content.
Embodiment 2
(1) select general purpose polystyrene (GPPS) (666D, Beijing Yanshan Petrochemical) as brittle layer matrix material.By double screw extruder extruder extruding pelletization, dry.
Double screw extruder extruding and pelletizing process parameter:
Processing temperature sets: a district, 2nd district, three district's temperature respectively 160,185,190 DEG C, and head temperature is 185 DEG C; Screw speed: 300 revs/min; Feeding: 8Hz; Pelleter pulling speed: 50-60 rev/min.
(2) polystyrene (GPPS) (666D is selected, Beijing Yanshan Petrochemical) as matrix material, styrene butadiene styrene block copolymer (SBS) (SBS) (4452, Beijing Yanshan Petrochemical) is as toughener, and GPPS/SBS mass proportioning is 60:40. Through double screw extruder extruding pelletization, drying, preparation GPPS/SBS blend is as ductile layers.
(3) fragility GPPS and toughness GPPS/SBS blend are put into respectively in the extruder A and extruder B (see Fig. 1) of the microbedding co-extruder being made up of extruder A, B, distributor C, layer multiplexer D and outlet mold E disclosed in Chinese patent CN101439576A, the rotating ratio regulating GPPS brittle layer and GPPS/SBS blended layer extruder is 5.0:6.0, and each section of temperature of extruder controls respectively at 160-185-190-190 C and 120-185-190-190 C. After material melts plasticizing in extruder, two strands of melts are made to overlap in distributor C, flow out from outlet mold E after the cutting and layering superposition of 7 layer multiplexer D, wherein distributor C, layer multiplexer D and outlet mold E temperature be about 185 DEG C, traction then through the compacting of tri-roll press machine and traction machine, can obtaining 256 layers from outlet mold extrusion and replace laminar composite (referring to Fig. 2), after testing, in this composite, the total content of toughener SBS is 27wt%. After testing, the room-temperature impact strength of this composite is 175J/m, and bending strength is 36MPa, and hot strength is 35MPa.
Comparative example 2
(1) selecting general purpose polystyrene (GPPP) (666D, Beijing Yanshan Petrochemical) as matrix material, styrene butadiene styrene block copolymer (SBS) (SBS) (4452, Beijing Yanshan Petrochemical), GPPP/SBS mass proportioning is 70:30. Through double screw extruder extruding pelletization, dry, prepare GPPP/SBS blend.
(2) use an extruder A in microbedding co-extruder disclosed in Chinese patent CN101439576A, close extruder B. The GPPP/SBS blend that quality proportioning is 70:30 is implanted sequentially extruder A, and the rotating ratio controlling extruder A is 5.0, and each section of temperature of extruder controls respectively at 120-185-190-190 C. After material melts plasticizing in extruder, make melt after flowing through distributor C, flow out from outlet mold E after the cutting continuously and layering superposition of 6 layer multiplexer D, wherein distributor C, layer multiplexer D and outlet mold E temperature be about 185 DEG C, then through the traction of the compacting of tri-roll press machine and traction machine, the common GPPP/SBS blend from outlet mold extrusion can be obtained.
Then adopt identical condition, prepare the common blend of GPPP/SBS that SBS content is 40wt%. After testing, SBS content is the room temperature notch impact strength of the common GPPP/SBS blend of 30wt% is 70KJ/m2, bending strength is 26MPa, and hot strength is 25MPa; SBS content is the room temperature notch impact strength 190KJ/m of the common GPPP/SBS blend of 40wt%2, bending strength is 23MPa, and hot strength is 20MPa.
Performance comparison from above-described embodiment 2 and comparative example 2, SBS total content is the room temperature notch impact strength room temperature notch impact strength close to the common blend that SBS content is 40wt% of the soft or hard alternate multiple composite of 27wt%, room temperature notch impact strength far above the common blend that SBS content is 30wt%. and the bending strength of the soft or hard alternate multiple composite that SBS total content is 27wt% and hot strength are also high than the bending strength of the common blend that SBS content is 30wt% and hot strength, especially far above the bending strength of the common blend that SBS content is 40wt% and hot strength.Visible, brittle layer prepared by the present invention and ductile layers replace the polystyrene based composites of stratiform arrangement and achieve brittle-ductile transition under relatively low SBS content, impart the impact flexibility that composite is more excellent, and the layer structure that soft or hard is arranged alternately also makes material while obtaining excellent toughness, maintain good rigid nature, it is thus achieved that the polystyrene based composites of excellent combination property. The formula of embodiment 2, Thickness ratio and the number of plies can be adjusted according to actual needs, and then obtain the polystyrene-based soft or hard alternate multiple composite of different SBS content.

Claims (4)

1. a polymer-based composite with excellent toughness, it is characterised in that this composite by following polymer-based brittle layer material and ductile layers material through melt extruding, n stratiform overlapping and formed 2(n+1)Layer soft or hard co-continuous layer structure composite alternately:
(1) described polymer-based brittle layer is identical with the matrix of ductile layers, selects the one in the polypropylene of poor toughness, polystyrene, polrvinyl chloride;
(2) toughener of described polymer-based ductile layers and matrix should have the relatively good compatibility, it is possible to select the one in polyolefin elastomer, EP rubbers, ethylene propylene diene rubber, styrene butadiene styrene block copolymer (SBS), chlorinated polyethylene, methyl methacrylate/butadiene/styrene copolymers, acrylonitrile/butadiene/styrene copolymer;
(3) in described polymer-based ductile layers, the consumption of toughener should more than the brittle-ductile transition point content of this toughened system.
2. prepare the polymer-based composite described in claim 1 with excellent toughness for one kind, adopt by extruder (A, B), allotter (C), the microbedding co-extruder that layer multiplexer (D) and outlet mold (E) are constituted, it is characterized in that first preparing fragility macromolecule layer material and toughness macromolecule layer material, then polymer-based brittle layer material and ductile layers material are put into respectively the two extruders (A of microbedding co-extrusion device, B) in, after fusion plastification, make two strands of melts overlapping in allotter (C), after the cutting and superposition of n layer multiplexer (D), flow out from outlet mold (E), traction then through the compacting of tri-roll press machine and traction machine, obtain 2(n+1)Layer is by the alternatively distributed polymer-based composite of brittle layer and ductile layers.
3. preparation according to claim 2 has the polymer-based composite of excellent toughness, it is characterised in that in soft or hard alternate multiple composite, toughener total content can be adjusted by the content of toughener in the thickness ratio of control brittle layer and ductile layers and toughness polymer-based composite layer.
4. the preparation according to Claims 2 or 3 has the polymer-based composite of excellent toughness, it is characterised in that the thickness of brittle layer and ductile layers is adjusted than by the rotating ratio of control two extruders (A, B).
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